Aliphatic olefins and cyclic process for manufacture thereof



March 14, 1950 L. F. BROOKE ETAL 2,500,307

' ALIPHATIC DLEFINS AND CYCLIC PROCESS FOR MANUFACTURE THEREOF Filed April 5, 1947 3 Sheets-Sheet l l\ Q g u 2 m N 1 I i :1 Q gQ ug 'u k & g '3 :3. r 3 a ,L E F I 4 Q do '0 N 9 Q Q Lloyd Brooke a W/Y/I'am 5. E/we// N m Richard L Meier ATTORNEYS March 14,1950 L. F. BROOKE EIAL 2,5 0, 7

ALIPHATIC OLEFINS AND cycuc PROCESS FOR MANUFACTURE THEREOF Filed April 5", 1947 s Sheets-Sheet 3 k "a I lo a;

Q Q Q ,zgm V\ i 6: -q- 77/19 3791.? w N H M sen/ans w -Ui aouvaa tU- IIF g I I I a )CDR W Q :1 h I g g uvvavrons Q Lloyd F Brooke William E E/we// Q m Richard L. Meier m A TTORNEYS Patented Mar. 14, 1950' ALIPHATIC OLEFINS AND CYCLIC PROCESS FOR MANUFACTURE THEREOF Lloyd F. Brooke,

Berkeley Highland Terrace, and

William E. Elwell and Richard L. Meier, Berkeley, Calm, assignors to California Research Corporation, San Francisco, Calif., a corporation of Delaware Application April 5, 1947, Serial No. 739,612

Claims.

This invention relates to hydrocarbon compositions consisting at least in major proportion of a mixture of aliphatic mono-olefins, said compositions having certain molecular weight distributions, and to a process of producing the same. More particularly, the invention involves the production of aliphatic mono-olefin mixtures in the C12 to 015 m0 ecular weight range and with controlled chain branching to obtain increased resistance to decomposition or fragmentation.

The present application is a continuation-inpart of our earlier application Serial No. 671,382, filed May 21, 1946, entitled Aliphatic olefins and manufacture thereof."

An object'of the invention is to produce allphatic mono-oleflns of branched-chain structure and improved resistance to fragmentation in the presence of anhydrous hydrofluoric acid under alkylating conditions.

Another object of the invention comprises the production of mixed aliphatic mono-olefins having a molecular weight distribution capable of yielding a superior detergent on further processing and of resisting decomposition or chain fragmentation during such processing.

Additionally an objection of the invention comprmes the production of branched chain monoolefins capable of resisting chain fragmentation during conversion to phenyl alkanes.

A still further object of the invention is to provide a process of producing in high yield a mixture of branched=chain alkenes resistant to fragmentation and having a molecular weight distributionv within the C12 to C15 range particularly adapted for the manufacture of detergents.

To improve operation of a cyclic polymerization process by minimizing continued and incremental reduction in conversions of monomer olefin to polymer olefin which is otherwise encountered in cyclic processes for manufacturing olefins from propylene is an additional object of this invention.

It is also an object to provide a method of reducing required recycle rates for any given conversion of monomer, or conversely for increasing productive capacity for any given recycle rate in a cyclic process for converting propylene into a mixture of oleflns boiling above about 325 F. and below about 520 F.

Other objects and advantages of the invention will be apparent from the followingdescription and attached drawing.

It has been discovered that aliphatic monooleflns satisfying the foregoing objectives can be obtained by mixing propylene with a C6 to C11 olefin of the type hereafter described and polymerizing the mixture in the presence of an acid polymerization catalyst to produce a mixture oi mono-olefins by interpolymerization. The re-= sulting mono-olefinic interpolymers are characterized by branched chain structure which has marked resistance to fragmentation in the presence of anhydrous hydrofluoric acid and by a molecular weight predominantly in the (312 to C15 range which, upon proper fractionation, givm a high yield of mono-oletlns with a molecular weight distribution in the C1: to C15 range. Further, it has been found that the mono-olefins thus obtained in the 012 to C15 range comprise a complex mixture of'compounds having a structure and a molecular weight distribution within this range which is particularly adapted to the manufacture of phenyl alkanes and of very efiective synthetic detergents by conversion of the even more complex mixture of phenyl alkanes to the corresponding sulfonates.

The C6 to C11 oleflns with which the propylene is interpolymerized in accordance with this invention are exemplified by straight-chain olefins such as n-hexene-l, n-heptene-l, n-octane-l, n-nonene-l, n-decene-l, or mixtures thereof. Other suitable olefins which are substantially straight-chem in structure comprise a complex mixture of C6 to C11 olefins obtained by fractionation from cracked paramn wax in accordance with known procedures or by fractionation of olefins from the hydrogenation of carbon monoxide by the well-known Fischer-Tropsch process.

Despite the fact that (l) branched chain C1: to Cm olefin structures of the type obtained from butene-l, butene-2, and isobutene polymers are relatively unstable and subject to large losses by fragmentation in the presence of hydrofluoric acid under alkylating conditions; and (2) notwithstanding that branched-chain structures are obtained in propylene polymerization and might be predicted to yield correspondingly unstable olefins, it has been discovered that C1: to C olefins having marked resistance to fragmentation in the presence of hydrofluoric acid under alkylating conditions may be obtained by polymerizing 1.0 liquid volume of propylene in admixture with at least about 0.2 and more desirably 2.0 to 10 parts by liquid volume (based on the propylene) of C6 to C11 olefins consisting essentially of polypropylene or interpolymers of propylene and ethylene. About 3 to-5.5 liquid volumes of Co to C11 oleflns to 1 volume of liquid propylene feed is presently preferred. From the foregoing it will be apparent that the Co to C11 olefins with which the propylene is interpolymerized may range from normal olefins having no chain ramification to olefins having polypropylene chain ramification. In general, polypropylene chain ramification is characterized by a straight-chain structure with only methyl groups as side chains,

the side methyl groups being x/3+l in num- During the foregoing copolymerization of propylenes with Cc-Cu olefins specifically exempli-= fied by olefins of polypropylene structure, all of the copolymer product is not in the desired high or molecular weight range, that is, boiling above 325 and preferably from about 360 to about 52W 3:. On the contrary, there is formed, very substantial quantities of light polymer comprising C11 and lower olefins boiling below 360 F., for example. To convert these light polymers to the desired higher molecular weight range prod uct, a cyclic process is needed, namely, one in which C11 and lower polymers arereturned to the polymerization zone for further conversion to the CHE-C16 product.- Preferably the light C11 and lower polymers are returned again and again a sufflcient number of times to be entirely consumed in the polymerization operation. This lat ter type of cyclic operation is herein termed re cycle to extinction! When one attempts to split the polymer reaction product at 356 F., for example, and recycle the more volatile fraction. (C11 and lower) an entirely unpredictable difidculty is encountered.

The system initially operates satisfactorily but as recycle continues conversion steadily drops and the volume of recycle increases correspondingly until the plant has little, or at best greatly reduced, capacity for conversion of fresh propylene feed. It might be assumed that the dimculty is due to various factors including, for example, suggestions that the lighter polymer will not copolymerize further with the fresh proylene feed imlzed by rejection of a selected hydrocarbon fraction from the polymer reaction products.

Although the mechanism of the phenomenon is not presently understood, it has been discovered that in the foregoing type of cyclic process, saturated hydrocarbons are formed in sufllcient quantity to build up in the system and interfere with the desired conversion of monomer olefin to polymer olefin. The high levels which saturate formation may reach are illustrated by continuous recycle of Cu and lighter olefins with continued build-up of saturate hydrocarbons, wherein the recycle stream may reach a saturate content of 60% or greater.

Additionally, it has been found that the saturated hydrocarbons formed in the cyclic operation have an unpredictable molecular weight distribution in the recycle stream. A typical mo lecular weight distribution of saturates in the Ca to C11 range is illustratedby the following analyses of 10% distillation cuts taken on a recycle stream boiling from to 350 F.

Volume Number Distillation Cut SPercc-ntd &9} 2 3E233 atumte Atoms 47 39 G. 4 45. 7 99 7. 1 43. 3 113 3. 1 36. 1 121 B. 7 36. 3 9. 3 33. 8 133 9. 5 28. O 134 9. 6 1S. 3 10. 0 9. 5 10. S 3. O 159 11. 3

Accordingly, the present. invention involves the discovery that loss in conversion and increase in recycle ratio can be minimized and controlled in the foregoing processes-by discarding a fraction comprising saturated hydrocarbons formed in the polymerization zone. The saturated hydrocarbons may be removed and discarded either from the entire polymerization eiiluent or from a por-= tion thereof such as the light recycle stream. One method of diminishing saturate buildup is to bleed out a portion of the light; recycle stream. However, this method is relatively non-selective, and methods yielding greater selectivity are preferred. Selectivity may be based either on mo- \7 lecular weight distribution or on diiferences in properties of the saturated paramnic hydrocarbone and the unsaturated olefinic components. Thus, suitable highly selective methods for removing the saturated hydrocarbons are liquid phase selective solvent extraction and, alternatively, selective adsorption of unsaturates on silica gel or the like.

Although somewhat increased capacity will result from the foregoing highly selective removal of substantially all the nonpolymer hydrocarbons formed in the polymerization operation, such a complete removal frequently will be found sumciently expensive to warrant another type of op-' eration herein disclosed. Thus, selectivity may be based on distillation coordinated with molecular weight distribution of the saturates. It has been found that if C5 and lighter saturated hydrocarbons formed in the polymerization zone are discarded by simple fractional distillation, saturate buildup can be controlled satisfactorily. The C5 and heavier saturated components may be recycled. Surprisingly, enough, the return of these C6 and heavier saturates to the polymerization zone either suppresses formation of additional saturated hydrocarbons of similar molecscribed, the lower molecular weight saturated hydrocarbons are separated from the polymerization reaction mixture and the higher molecular.

weight components, for example, those retained in recycle stock boiling above 110 F. are returned to the polymerization zone. Such recycle of higher boiling non-polymer hydrocarbons together with olefin polymers of similar boiling range has been found to give a steady state operation in a continuous cyclic process with a saturate content of about 25% in the recycle stream. By accepting a propylene conversion of about 90% in such an operation, the saturate discard can be efiected very simply, namely, by eliminating lighter than Cs reaction components in a distillation stripper for the reaction eliiuent. when and if somewhat higher recycle ratios are acceptable, the distillation stripper may be operated to split the saturated hydrocarbon fraction in the C5 boiling range so that C4 and lighter hydrocarbons together with some of the C5 fraction are eliminated. A portion of the C5 together with higher boiling saturated compounds flow back with the recycle stream to the polymerization zone.

The amount of light non-polymer hydrocarbon formation in per cent of propylene reacted in a typical steady state operation of a cyclic process is as follows:

Per cent Butenes 0.34 Butanes 3.16 Pentenes 2.70 Pentanes 5.0

As previously stated, the mixed C12 to C15 oleflns of this invention are much more resistant to fragmentation by hydrofluoric acid under alkylating conditions than are other more highly ramifled branched-chain. oleflns, such as the polybutenes inthe same molecular weight range. This is illustrated by the fact that in the hydrofluoric acid catalyzed alkylation of benzene with the polybutene type olefins to form alkyl benzenes, almost 50% loss to lighter than C12 alkylate occurs by reason of fragmentation of polybutene -olefins and formation of light alkyl benzenes from the decomposed olefins, and less than about 30% of C1: alkylated benzene yield is obtained. Conversely, yields of 80% or more of monophenyl C12 alkanes are obtained with the C12 polypropylene ramiiled type olefin and less than about 12% loss to light alkylate occurs under corresponding alkylating conditions.

An additional new and unpredictable property of the polypropylene ramified type olefins coniprises the fact that the resulting phenyl alkane derivatives are sufficiently stable to be substantially completely sulfonated in high yield without material formation of unsulfonated residues, color bodies and the like. This stability is important since relatively pure phenyl alkane derivatives can be obtained without the necessity of expensive purification treatments. For example, a phenyl substituted alkane of the C12 polypropylene rammed type will yield approximately 100% of the corresponding sulfonic acid of good color and substantially free of unsulfonated residue. 0n the other hand, sulfonation of benzene which has been alkylated with a C12 polybutene under comparable conditions has been found to yield only about 74.4% of sulfonic acid containing 25.6% of unsulfonated residue which generally must be removed by purification treatment.

In the drawing, Fig. 1 is a diagrammatic flow sheet of a process and apparatus for preparing interpolymers, separating C12 and Clfi olefin fractions, and discarding saturated paraiIlnic-hydrocarbons formed during polymerization as herein disclosed.

Fig. 2 is a diagrammatic flow sheet of a simplified process and apparatus for preparing interpolymers of propylene and utilizing only those Cs-Cu olefins formed in the polymerization process for copolymerization with fresh propylene.

Fig. 3 is a schematic flow sheet of a process for preparing mono-olefins and for withdrawing saturates together with a portion of polymer by fractionation of recycle light polymer stream as well as by elimination of lighter saturates by stripping or stabilizing polymerization emuent.

A preferred process comprises continuously feeding propylene with Co to C11 olefins, desirably polypropylene, in the ratio of from at least about 0.2 liquid volumes of the latter olefin to 1 liquid volume of propylene to a polymerization zone comprising a fixed bed of a catalyst known in the art as a solid phosphoric acid catalyst. Preferred ratios of Cc-Cu polypropylene to liquid propylene feed are from 3 :1 to 55:1 as previously described. However, the Ce-Gn olefin may be selected from the group consisting of straightchain olefins and propylene polymers. The polymerization is effected at a catalyst temperature of from about 375 F. to about 500 F., preferably from. about 400 F. to about 460 F. The preferred catalyst is phosphoric acid (100% to 110% orthophosphoric acid) on a suitable porous support, such as kieselguhr or active carbon. Space rate is desirably from .02 to 2 volumes of liquid propylene per volume of catalyst per hour. Pressure may vary from 100 to 2,000 pounds per square inch gauge, 200 to 600 pounds per square inch being more desirable except that pressures of 250 pounds or less may tend to give lower rates of saturate formation. The polymer mixture is then withdrawn from the polymerization zone and fractionated to yield a mixed mono-olefin fraction having a molecular weight distribution in the C12 to C15 range. Suitable olefin mixtures have an initial boiling point of about 325 F. and an end point of about 520 F. at least about 50% of which boils above 380 F., or the polymer mixture may be fractionated to yield a C12 olefin go out having a boiling range from about 330 F. to

which boils within the range of from about 380 F about 420 F., at least about 50% of which boils above 350 F., and a C15 fraction having a boiling range from about 420 F. to about 510 F., at least about 50% of which boils above 450 F. A preferred mixture for the manufacture of monophenyl alkanes comprises a fraction having an initial boiling point of from about 360 F. to about 370 F., and an end point of from about 500 F. to about 520 F., at least about 80% of to about 440 F., and at least about 50% of which boils above 390 F. The foregoing boiling ranges are determined by a standard ASTM-DBG distillation.

Reference to Fig. l of the drawing will reveal that in this embodiment of the invention only the lighter or more volatile saturates formed in the polymerization zone are eliminated together with fixed gases. Thus, there is provided a polymerization chamber from which the reaction mixture is passed first to a stripper l I for removing only the lighter or more volatile hydrocarbons formed in the polymerization chamber to together with fixed gases and other light hydrocarbons present in the feed. The stripped reaction mixture then flows to a iractionator I2 for separating Cu and lower olefin polymers as overhead. A second fractionator l3 receives the bottoms from fractionator l2 and separates a Cu olefin mixture as an overhead fraction. Final fractionator M separates the bottoms from fractionator l3 into a C olefin mixture as overhead and heavier than C15 hydrocarbons as bottoms.

More specifically, C6 to C11 olefins selected from the group consisting of straight-chain olefins and polypropylene are fed by way of inlet line L5 together with propylene by way of inlet line 36 to mixer ill. The resulting olefin mixture then passes through preheater l8 and feed line 9 to a fixed bed solid phosphoric acid catalyst in polymerization chamber 50. Steam also is introduced into the polymerization chamber by way of line in a quantity sufiicientto maintain a partial pressure of water vapor equal to that of the phosphoric acid catalyst in order to prevent dehydration of the catalyst which is maintained at the desired temperature. Intel-polymerization of the propylene with the C6 to Cu olefins is effected upon contact with the polymerization catalyst,

and the resulting mixture is then conducted by way of conduit 29 through heat exchanger is to stripper ii, where low boiling hydrocarbons are removed as overhead through line 22. The gases removed in the stripper H comprise mostly propane and propane together with other hydroi carbons containing, for example, less than five carbon atoms. The stripped gas flows through cooler 23 to collecting drum 2d, where uncon densed gases may be discharged through vent line 23. In order to control the temperature developed by exothermic heat of reaction in the polymerization zone, a portion of the cooled gases and of any condensate formed in drum 2:; may be conveyed by way of valve-controlled line 2'3 and introduced in the polymerized mixture as a diluent and cooling gas. However, this tends to increase saturate buildup in the cyclic system and it is, therefore, preferred to facilitate control of the reaction temperature by providing a cold feed inlet stream. For this purpose valve-controlled conduit 28 is provided for by-passing some of the reaction feed directly to the polymerization zone without preheating in heat exchanger it.

The stripped olefin mixture flows from the bottom of stripper H by way of conduit 29 to the first iractionator 52 where light olefin polymers, together with any saturated hydrocarbons, in the C6 to C11 range are separated as a vapor phase overhead which passes by way of outlet conduit through condenser 32 to condensate drum 33. Fractionation is controlled and improved by returning a portion of the condensate from drum 33 to iractionator l2 by way of valve-controlled reflux line 3 5.

In order to increase the yield of C12-C1s olefins, a cyclic operation is preferred. In the cyclic operation at least a portion of the (Ia-C11 olefins is returned by way of valve-contr0lled line 36 to polymerization zone ill to cause interpolymerizatlon of these lower polymers with the propylene feed to yield additional C1; to C15 oleflns. Excess Cc-Cu olefins may be withdrawn by means of discharge line 35. In addition to discarding saturates by means of stripper column ll, further increases in conversion and reductions in recycle rate may be obtained by treating recycle stream 36 to separate saturates from unsaturates or alternatively by treating the portion of Co to C11 olefins withdrawn by line 35 in a similar manner and returning the olefins' denuded of saturates to recycle stream 36. Suitable processes are known for separatin saturated aliphatic from unsaturated aliphatics in the Cs-Cu molecular weight range. Exemplary processes are liquid phase selective solvent extraction and, alternatively, preferential adsorption of unsaturated hydrocarbons on an adsorbent such as silica gel or the like followed by removal of the saturate fraction and recovery of the unsaturated adsorbed fraction.

The C12 and higher boiling oleilns pass downwardly through fractionating column 12 and out discharge line 31 through pressure-reducing valve 38 to fractionator 53 where a C12 olefin fraction boiling, for example, from about 330 F. to about 420 F. is taken overhead through condenser 30 and collected in condensate drum ll. This fractionation may be efiected under vacuum which is maintained through vacuum line 02 connected to a vacuum pump, steam ejector or other suitable means for maintaining the required subatmospheric pressure. A portion of the condensate may be returned as reflux to fractionator 63 through valve-controlled reflux line 03. It is sometimes found desirable to recycle another portion of the Cu: olefin cut by way of valve-controlled line i l through circulation pump 06 to mixer ill. The remainder of the C12 olefin cut is pumped through conduit 3? to storage 00.

The C15 and higher boiling olefins flow downwardly through fractionating column is and are discharged by way of line 09 through pressurereducing valve 5i into fractionator it where a C15 olefin fraction boiling, for example, from about 420 to about 500 F. is taken overhead through condenser 52 to condensate drum 53. A portion of the condensate may be returned to fractionator M by way of valve-controlled reflux line '52 and the remainder pumped to storage through line 55. Bottoms from iractionator it are discharged through outlet line 51.

It is preferred to operate fractionating column 50, as well as column i3, under vacuum in order to avoid deterioration of the C12 to C15 olefins by decomposition or further polymerization. Desirably fractionator i6 is maintained at a higher vacuum than fractionator is by means of vacuum line 58 connected to a suitable device for maintaining reduced pressure, such as a vacuum pump or steam ejector.

Exemplary polymerization conditions in the process of Fig. l are:

Temperature of fresh feed- 350-425 F. Temperature of catalyst 3'75-500 F. (preferably 400- 460 F.) Pressure 200-600 lbs/sq. in. Propylene feed .02-02 V./V./hr. Catalyst -l10% orthophosphoric acid on kieselguhr A typical propylene-ethylene feedstock will contain other normally gaseous saturated hydrocarbons in proportions, such as the following:

Volume Per Hydrocarbon Gent (Vapor) Ethylene Ethane Relative Vol- Relative Vol- Per Cent Cu to ume Propylene ume Cu to C15 Olefin In Feed in Feed Polymer (Based on Propylene Polymerized) In these runs the average temperature of catalyst was 430 F., pressure, 200 pounds per square inch gauge, and propylene feed rate, .032 V./V./hr. Higher pressures increase the yield of Cir-C15 olefin interpolymers as illustrated by the following data:

s R t c t h d pace 8 e, on use Pmssme V./V./hr. on Propylene Feed 200 lbs/sq. in 074 81 500 lbs/sq. in 074 110 200 lbs/sq. in .032 92 500 lbs./sq. in .032 121 These yields are based on fresh propylene feed in the copolymerization of Fig. 1 without recycle of light polymer. In this situation it is preferred to operate the process at 400 to 600 pounds per square inch pressure. In these latter runs, average catalyst temperature was 430 F., and the ratio of Cs-Cn olefins to propylene was approximately 2.2:1.

Referring to the how sheet of Fig. 2 a mixture of propylene and ethylen containing some fixed gases is introduced by way of line 60 through heat exchanger 0!, preheater 02 and inlet line 30 to a fixed bed solid phosphoric catalyst chamber 63. Cu and lower olefins previously formed by the polymerization of a mixture of ethylene and a propylene are simultaneously passed from recycle line 60 into heat exchanger 6| and pass with the feed olefins through the polymerization catalyst where mixing and interpolymerization with the fresh propylene and ethylene feed is effected. Water preferably as steam is injected into the catalyst chamber by injection pump 65 through line 60 to maintain a partial pressure of water vapor which will avoid dehydration of the phosphoric acid catalyst. .A branched water or steam inlet 06a likewise may serve to introduce controlled amounts of H20 into the hydrocarbon feed for similar purposes. The interpolymers of the fresh propylene feed with the recycle C11 and lower olefins are discharged from the bottom of the polymerization chamber by way of outlet conduit 68 through filter 69, heat exchanger 8|, cooler H and line 12 to stripping or stabilizing column 13. V

In order to control temperature of the feed and reduce reaction temperature in the polymerization zone regulated portions of the fresh olefin feed flow through by-pass line 01 and join the remainder of the reaction feed between preheater 52 and reactor 83.

The crude interpolymer is stripped andstabilized in column 13 to separate a C5 and lighter hydrocarbons fraction as an overhead which is discharged through conduit ll. As previously explained these Cs and lighter hydrocarbons include saturated butenes and pentanes as well as minor amounts of butenes and pentenes formed in polymerization reactor 03.

Co and heavier olefins together with corresponding saturates flow downwardly through stabilizer l3 and outlet conduit 16 to recycle still and fractionating columnll. Reboiler l0 supplies heat to stabilizer column 13 for driving on the C4 and lighter hydrocarbons together with at least some Cs hydrocarbons in the stripping operation.

In recycle still ill, to which heat is supplied by reboiler as, the 06-011 olefins are separated as an overhead fraction boiling for example below about 360 F. This overhead fraction passes from the top of the iractionating column of still Tl through outlet F0 and condenser 8i to a condensate drum 02. A portion of the liquid phase olefin condensate may be returned to recycle still or frac= tionating column H by way of a valve-controlled reflux line 00. A steam operated circulation pump 83 is provided in the discharge line from condensate drum 82. Cs-Ou olefin condensate is pumped from drum 02 through recycle line 0% to polymerization chamber 53 through heat exchanger EE and preheater as as previously disclosed.

C12 and higher olefins are removed from the bottom of recycle still ll through outlet 80, cooler 8? and heavy polymer discharge pump 80. This heavier polymer product comprises primar ily C12-C1s olefins but contains some higher boil-=- ing components. In order to obtain the preferred mixture, as previously disclosed, this heavy poly mer is fractionated to obtain an overhead olefin out having an initial boiling point of from about 360" F. to about 370 F. and an end point of from about 500 to about 520 F., although an end point of 480 F. may be used. It is also preferred that about of this olefin cut boil within the range of 380 F. to about 140 F. The separation of this Cm-Crs olefin cut preferably is eiiected under vacuum in a iractionatin-g column; reduced pressure is maintained on the system. Distillation bottoms containing some diolefins and having an initial boiling point of from about 500- 520 F. are thus eliminated and detrimental effects on stability of the polymer in hydrogen fluorid alkylation reactions are thereby reduced or avoided.

A typical stock balance for operation of the process and apparatus ofFig. 2 with recycle to extinction is given in Table 1. Reaction conditions for this operation are propylene space rate of .041 liquid volumes per volume of catalyst per hour, reactor outlet temperature-460 F., and reactor pressure of 250 pounds per square inch gauge. Reactor conversion of propylene was about and of ethylene about 20%. Nonaeoaaov polymer hydrocarbons formed in the reactor based on propylene converted were butene- 0.34%, butane-3.16%, pentene-2.70%, Den ta'r'ie5.0%. For steady state operation, with recycle to extinction the recycle stream contains t2 the column through reboiler 521. The stripped reaction mixture flows from stabilizer I through line I28 to recycle still and fractionatlng column I29. The polymer mixture is here fractionated into a light polymer overhead and a so-called only about saturates. heavy" polymer bottoms fraction. This split I TABLE I Quantities in lbs/day Stream No. H

nvy Component Feed Polymer 8,500 8,500 00,200 00,200 10,400 10,400 137,700 12. ,700 4,380 1,580 13,150 5,050 8,190 1,500 CIH12 15,540 2,040 Light ole (110360F.) 570,000 570,000 570,000 Heavy Po ymer (360+) H 54,520

Total aoaoso 000,000 000,000 906,080 251,501

In Fig. 3, propylene feed containing propane is introduced to the system through main line l0! and flows to polymerization reactor IIO through branched feed line I02, heat exchanger I03 and preheater I04 in line I05. Previously formed light polymer from recycle line 108 is blended with propylene feed. Temperature control is afforded by feed by-pass line I01 for introducing controlled amounts of cool propylene feed into the heated portion of the hydrocarbon feed of line I05. The composite feed stock may enter reactor III! either by way of main composite feed line I06 or a second by-pass composite feed line H2. This dual feed into reactor IIO affords control of temperature distribution in the catalyst bed and reduces a tendency to form excessively high temperatures in a hot spot in the reaction zone otherwise occasioned by fast reaction of a large portion of the-entire olefin feed in a limited zone of the reactor.

The downwardly flowing mixture of propylene and recycled light polymers are intermingled and copolymerized in reactor IIO, and the reaction product flows from outlet H3 through filter IId, preheater I03, cooler H6, and line .lI'l to stripper or stabilizer II 8. C3 and lighter hydrocarbons are stripped from the reactionmixture in stabilizer II8 operated under reflux conditions.

The overhead fraction of C3 and lighter hydrocarbons flows by way of outlet IIQ through refrigerated condenser I25 to condensate drum I22. Regulated amounts of C3 hydrocarbons are discharged by way of outlet line 423. Reflux on stabilizer H8 is maintained by circulation pump I25 and valve-controlledrefiux line I20.

Concentration of propylene in the feed to the polymerization reactor is regulated by recycling controlled amounts of C3 and lighter hydrocarbons, mainly propane, from condensate drum 122 through line I26 to polymer recycle line I00. This recycle of propane serves as a further control on reaction temperatures and rates in polymerization reactor I I0.

Steam or water is introduced into the feed by way of steam operated injection pump I09 and H20 inlet line I to hydrocarbon feed from line 502.

C0 and heavier hydrocarbon flows downwardly through stripping column I I8 and the lighter hydrocarbons are distilled out by heat supplied to Olefin polymer boiling above 325 F. and pref erably above 360 F. is stripped of the light polymer product and flows downwardly through still I29 through outlet I32, steam operated circulation pump I33, cooler I34 and heavy polymer product line to further fractionation (not shown). As previously disclosed, this heavy polymer fraction consists primarily of C12-C15 monoolefins, but contains heavier polymers which are eliminated by a further distillation to yield the preferred C12-Cl5 cut as an overhead fraction boiling below about 520 F.

Referring back to the light polymer overhead from recycle still I29, this polymer is returned to polymer recycle line I08 by line I443. saturate buildup in the system is controlled by bleeding at least a portion of the recycle polymer through heat exchanger I 46 to paralfin rejection still Ml. Reference was previously made to the discovery that the saturate or parafiin hydrocarbons formed in reactor 0 are not uniformly distributed in molecular weight and the process of Fig. 3 may be operated to take advantage of this discovery by rejecting as overhead the more volatile components of the light polymer recycle thereby eliminating objectionable paraffin or saturate buildup at a minimum cost in light polymer rejection. Likewise, parafin rejection still I41 may be operated to reject C5 and lighter hydrocarbons with return of Cs and higher polymer hydrocarbons, together with corresponding saturates, to the recycle stream. In this latter type of operation by-pass line M5 may be closed to divert all recycle stock through heater M 1 and line I40 to still I07. Higher saturates retained in the recycle stream are decomposed or serve to suppress inordinate saturate buildup in the greater than C5 molecular weight range.

However, as here shown, the process of Fig. 3 is operated to take a portion of the light polymer overhead, for example Ca and lighter, more desirably C6 and lower hydrocarbons together with the corresponding saturates or parafins. This 7 overhead fraction flows through outlet I510, con- 13 denser I49, reflux drum iii, circulation pump I52 and cooler I as polymer reject. Reflux on still 1 is maintained by valve-controlled reflux line I.

Polymer reject may be discarded or, if desired,

14 F. was analyzed by two methods and the diolefln content found to be in the range of 16 to 26 mol per cent conjugated diolefin content is low, i. e. less than 5%.

5 When desired both the conjugated and nonthe, unsaturated polymer portion may be s paconjugated diolefins may be eliminated for the rated from the saturated paraflin portion by seproduction or monophenyl alkane. Silica gel adlective solvent extraction, silica gel adsorption sorption processes, for example, may be utilized or the like in order to eliminate the paramnic for separation of conjugated di-oleflns prior to saturated components only. The extracted or alkylation with benzene. It may be found more adsorbed olefins freed of their saturated com= economical, however, to eliminate dioleflns by Q1- ponents are then returned to the system as a kylating benzene with the mixturetoform monorecycle stock. phenyl alkanes with the mono-oleflns and di- The less volatile portion of the light polymer phenyl alkanes from the diolefins, followed by recycle stock flows downwardly through paraflin separaflun of th monod s h y a rejection still it! to which heat is supplied by pounds by distillation. The monophenyl alkane reboiler I56 and after being fractionated flows compounds are taken as overhead and the di= through outlet I57 and heat exchanger i to rephenyl compounds separated therefrom as hotcycle line 10s by way of line I43 and steam-opert m ated circulation pump I58. The amount of saturate formation and the re- The relative proportions of light recycle stock lated djolefln formation occurring i t o returned dire ly to the feed on One hand and merization zone may be controlled and redu IF-passed to paraffin rejection still 141 on the to some extent by manipulation or adjustment o h r h n s Controlled by any Suitable means in of reaction conditions. One of the most siby-pass li e 15 a s the inlet d outlet. of cant variables is pressure. High pressures, for preheater IM- Thus, Suitable Proportiomng example 500 pounds per square inch gauge, may valves may e ns r n lines and M5 to tend to increase the rate of saturate formation Vide the two Streams as desiredas compared with lower pressures, such as at- Table II is an exemplary stock balance for an mospheric to 250 pounds per square inch gauge Operation the Process and apparatus of At either high or low pressures, the severity of Exemplary reactionconditions are: pressure-500 operating conditions as indicated by propylene Pmmds i Square react tempera conversion can be correlated with saturate fortm'Hso olefin space liquid mation, that is, the more severe the conditions Volumes of propylene per Volume of catalyst per or the higher the propylene conversion rate, the hour- ApprPximate overall mversion through greater is the rate of saturate formation. Con the system is: t y 2%. Propylene-90% version rates of 70-90% are presently preferred. with reactor conversions at ethylene-15.6%, and The ratio of saturates formed to heavy polymer Prpy1e1n1e 74-8%- Rates of and C5 hydro" formed appears to decrease with decreasing procal'bon Iormation in terms of per cent of prowl pylene concentration in the feed when dilution is ene reactant are approximately: with C3 and lighter saturates. B he ggi The recycle ratios herein before given as pre- H De ferrecl are for operations in which the re- Butane cycle stream contains some saturate as in the Pentene specific examples on which stock balances are tane 9.39 Pen g ven. The ratios are in terms of polypropylene Catalyst is orthophosphoric acid on kieselguhr. in the recycle stream as distinguished from gross TABLE II Quontttiesinlba/iir.

Stream No.

Poly- Heavy Component Feed mer Poly- Relcycle Re ciyscle Reggae 117 123 128 M2 146 157 145 Reject mer om 1.900 2,170 2,173 0,111.-- 1,648 2,318 1,050 (33111... 6,467 11,697 11,697 0133... 11,255 13, 550 3,421 01H 11,600 39,800 39,800 C1511- 24 1, 518 l, 524 01B 208 3, 967 4, 567 C5H10 1,020 2,133 0111"". 3,005 3,955 Light Polymer (110- 3 irdififiba 82,946 82,986 8,383 3,3 3 rem 33,336 44,734 84,527 129,261 1s2,591 1e2,59723,a0 94,3s3 86,000 28,355 27,382 57,145 1,473 8,383

The formation of paraifins from olefins in the recycle hydrocarbon stream. In general, the polymerization reactor is accompanied by the higher the polypropylene content of the recycle formation of less saturated material. This less stream, the lower the optimum recycle ratio of saturated reaction product appears to some expoypropylene to fresh propylene feed. (Note tent as a highly oleflnic tar or coke on the cat that this lower ratio is in terms of polypropylene alystand some exists as dior polyolefins in and, therefore, is over and above the reduction the predominantly mono-olefin polymer fraction. resulting from more decrease in saturate con- Asample of propylene polym r boiling above 350 te t) Thug 1e mam M- -sg aeoasor the recycle stream, a recycle ratio of about 2.0 to 2.5 by volume of polyproylene to 1 liquid volume of propylene feed is preferred.

Reference has been made to the fact that the molecular weight distribution of the interpolymers produced by the invention in the C1: to 015 range is especially advantageous for certain purposes, such as the production of synthetic de- 1 These are vapor line temperatures.

A blend of from 60% to 80% of the foregoing C12 fraction with from 40% to 20% of the C15 fraction upon conversion to a monophenyl alkane yields a sulfonate detergent superior to either fraction alone. A single C12 to C15 cut with 80% boiling above 380 F. and 50% above 390 F. as in column 4 above, is superior even to the foregoing blend in this respect.

It is virtually impossible to define in terms of precise chemical structure the new mixture of olefins obtained according to this invention. However, the ratio of corrected optical density of the polymer at about 10.35 mu to corrected optical density at about 11.23 mu is definitive of significant chemical type structures characterizing the mixture of components and is indicative of the relative proportions of diiferent types of components contained therein as will be apit diflerent chemical groups are often great enough to permit positive identification oi the principal functional groups in a molecule. Thus, by irradiating a chemical compound or a mixture of compounds with infrared light to obtain the com-' plete infrared absorption spectrum of the composition, one may obtain the sum of the contributions from all of the characteristic chemical or functional groups in the material and thereby determine its principal type components or features of chemical structure. Many of the correlations which have been made between molecular structures and frequencies of absorption bands are given in Table 111.

TABLE III 1 Group Wave Length Ma 0-H 3. s 8;}? it 8E3. it

& 10.0 and 11.6

R-C=OR' H R--C=( 3 it 1k 11.25

R--G=O-B 1 Thompson and Tarkington Trans. Faraday Soc. 41, 246 (1945).

It has been found that infrared absorption and optical density in the 10.35 and 11.25 bands char acterize olefin polymers having high resistance to fragmentation and degradation by anhydrous hydrofluoric acid.

The following data are illustrative:

TABEE IV C]: Cm Mixed C12 012 Propylene Butane Butene-1 Butane-2 Po ymer Polymer Polymer Polymer D 10.35 mu 1. 308. 0. 783 0. 936 0.835 D.: 11.25 mn 1.020 1.49 1.173 1.04 =11 factor 1. 28 0. 525 0.191 can 0 Emol 10.35 mu=Mol. Extinction Coefficient 13. 08 7. 83 9. 36 8. 85

diminishing the intensity of, the light which is transmitted. Likewise, each pair or characteristic group of atoms in a molecule has its own natural modes or frequency of vibration. The difference between the absorption frequencies of These data show that the ratio of corrected optical density (Do) at 10.35 mu to corrected op tical density to 11.25 mu is greater than 1 for olefin chains of polypropylene structure, whereas non-equivalent oleilns, exemplified by polymers of the butenes are characterized by a value of less than 1 for the same ratio. This ratio of corrected optical densities at 10.35 mu and 11.25 mu is hereinafter termed R factor.

Likewise, the foregoing data illustrate the fact that the desired oleflns of polypropylene structure possess a molecular (Enrol) extinction coeificient greater than 10 and preferably greater than about 12 at 10.35 mu, whereas non-equivalent claims have a molecular extinction coeficient less than 10 in this band.

The following test procedures are utilized for determining the above values.

Test procedure for determining R factor Using an infrared spectrometer equipped with Non-equivalency of different branched-chain olefins in the HF alkylation, oi benzene are illustrated by the following:

liquid cells of approximately 0.1 mm. in thickness, accurate optical density measurements of the olefin sample are made every .02 to .04 mu in the 10.35 mu absorption band (for example from 10.2 mu to 10.5 mu) and in the 11.25 mu absorption band (for example from 11.1 mu to 11.4 mu). An infrared spectrum is drawn plotting optical density as the ordinant 0. wave length as the abscissae. The molecular weight and specific gravity of the olefin sample are measured by the usual methods. The optical density values corresponding to the peak of the absorbed band near 10.35 mu and near 11.25 mu are read from the spectrum, and each is corrected to a molecular weight basis of iand a specific gravity of 1 as follows:

D 1) (measured X (Mol.wt.) 1)

(Specific gravity) X100 R factor is then determined as follows:

D., at 10.35 mu D, at 11.25 mu A value greater than unity for the R factor indicates a satisfactory propylene polymer and a polymer having a relatively high proportion of olefins with the structure:

An R factor less than unity indicates a polymer which is subject to degradation and fragmentation in the presence of active alkylation or condensation catalysts and shows that the polymer mixture contains a relatively high proportion of olefins having the structure:

Test procedures for determining molecular en:- tincta'on coefiicient The optical density of the olefin sample corresponding to the peak of the absorption band near 10.35 mu is obtained as in the test procedure for determining R factor. From this measured optical density the measured molecular weight of the sample and the measured specific gravity, culated as follows:

E 10.35 mu= D (measured at 10.35 mu) (M01. Wt.) IOOOX (specific gravity) X (thickness of sample in centimeters) Values greater than for Emol at 10.35 mu and preferably greater than 12 indicate a satisfactory polymer having a relatively high concentration of olefins of the structure:

' tions.

the molecular extinction coeficient is cal- I As previously indicated the exact chemical constitution of the compositions produced according to this invention cannot be precisely defined. However, the infrared absorption spectrum clearly indicates that the oleflns of polypropylene structure are largelyof the type:

i, i rather than n-o=o-n The C12 to Cu oleflns produced according to this invention are useful not only in the production of phenyl alkanes and sulionated derive-,- tives thereof, but are capable of other applica- For example, these polymers may be hydrogenated to produce long chain alkanes which, in turn, may be converted to alkyl sulfonates by chlorosulfonation according to the method dis closed in Reissue Patent No. 20,968, granted to Reed. The resulting sulfonates so obtained have valuable surface active properties. Further, the 012 to C15 olefins of this invention may be converted to the corresponding alcohols by any suit able process, such as a hydrochlorination oi the olefin bond and hydrolysis oi the resulting allryi chloride. Again, the C12 to C15 oleflns may be condensed with phenol by hydrofluoric acid or sulfuric acid catalysis to yield a corresponding alkyl phenol. These alltyl phenols are useful as such or may be converted to polyvalent phenates which are particularly well adapted for addition to hydrocarbon lubricating oils as a stabilizing or anti-ring sticking agent. Also, the olefinc may be alkylated with isobutene by sulfuric or hydrofluoric acid catalysis to yield saturated alkyl compounds. In short, the relative stability and resistance to fragmentation of the 012 to C15 oleflns herein produced adapt the compounds to preparation of derivatives containing relatively stable long alkyi chains having chain branching within controlled limits.

In the appended claims the terms tetramer fraction and "pentamer fraction are used to specify, respectively, the fractions designated in this specification as 012 and C15 fractions. It is to be understood that the polymerization reaction does not necessarily proceed so smoothly or accurately as to yield only tetramers and "pentamers" or even only C12 and C15 hydrocarbons, but that the terms tetramer and "pentamer" are meant to-be descriptive of those olefin hydrocarbons present in the polymer product and boiling in the defined range which embraces the boiling points of various isomeric C12 and 01s polymer hydrocarbons present therein.

The character of the invention and the value 5 neither is to be considered as iming correand the results given, butsponding limitations upon the scope 1. A cyclic process for producing a mixture of branched-chain olefins boiling above '360 F. and

having an R factor" greater than 1, which comprises polymerizing a mixture of .propylene with a propylene polymer fraction boiling below 360 F. by passing propylene through a polymerization zone containing a solid phospheric acid polymerization catalyst at a temperature of irpm about 375 F. to about 500 F., separating from the reaction mixture 0. more volatile olefinic hydrocarbon polymer fraction boiling below 360 F., recycling at least about two liquid volumes of said more volatile polymer fraction per volume of propylene through said polymerization zone whereby conversion to polymeric olefins boiling above 360 F. tends materially to decline as said recycling is continued, and reducing said decline in conversion by selectively rejecting from the cycle a light hydrocarbon fraction boiling below 360 F. andcomprising at least C4 saturated hydrocarbons formed in the polymerization zone.

2. A cyclic process which comprises converting propylene to a mixture of polymeric olefins boiling above about 325 1''. and below about 520 F. by contacting propylene with an acid polymerization catalyst in a polymerization zone, separating from the reaction mixture a lower boiling' but normally liquid olefin polymer fraction, recycyling said lower boiling liquid polymer fraction to the polymerization zone, recovering from the reaction products a higher boiling mixture of polymeric olefins boiling above 325 F., and inhibiting decline in conversion rate to said higher boiling polymeric olefin mixture by rejecting from the polymerization cycle a fraction comprising saturated hydrocarbons formed in said polymerization zone.

3. A process as defined in claim 2 wherein said rejected fraction comprises saturated hydrocar bons within the C4 to Co range formed in said polymerization zone.

4. A process as defined in claim 2 wherein said rejection is by fractionation of the polymerization reaction mixture to remove a light hydrocarbon fraction containing saturated hydrocarbons within the C4 to Co range and formed in said polymerization zone.

5. A process as defined in claim 2 wherein said decline in conversion rate is inhibited by fractionating said lighter olefin polymer fraction to reject saturated hydrocarbons within the C4 to Ca range formed in said polymerization zone.

, 8. A cyclic process for producing a mixture of branched-chain olefins boiling above about 325 20 l". which comprises polymerizing a mixture of propylene with a propylene polymer traction boiling below about 360 F. by passing said mixture through a polymerization zone containing a phosphoric acid polymerization'catalyst at a temperature 01 from about 375 F. to about 500 F., separating from the reaction mixture more volatile but normally liquid olefin polymer hydrocarbons boiling below 360 F., recycling said more volatile olefin polymers through said polymerization zone whereby conversion to polymeric olefins boiling above about 325 F. tends materially to decline as said recycling is continued, and reducing said decline in conversion by rejecting from the cycle a light hydrocarbon fraction containing saturated hydrocarbons in the C4 to Cs range formed in the polymerization zone.

'7. A process as defined in claim 6 wherein said light hydrocarbon fraction is rejected by distillation of the polymerization reaction mixture.

8. A process as defined in claim 6 wherein said light hydrocarbon fraction is rejected by distillation of said .more volatile but normally liquid olefin polymer fraction boiling below 360 1".

9. A cyclic process for producing a mixture of branched chain olefins boiling above about 325 F. which comprises contacting propylene with an acid polymerization catalyst in a polymerization zone, separating from the mixture of polymers thereby formed a more volatile but normally liq-' uid fraction of lower boiling olefin polymers, re-

covering a less volatile fraction of higher polymeric olefins, said higher olefins boiling above about 325 F. and below about 520 F., recycling said more volatile polymer fraction to the polymerization zone, and inhibiting decline in conversion rate to said higher boiling polymeric olefin mixture by rejecting from the polymerization cycle a fraction comprising saturated hydrocarbons formed in said polymerization zone.

LLOYD F. BROOKE.

WILLIAM E. ELWELL.

RICHARD L. MEIER.

REFERENCES crrnn The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,181,640 Deanesly et a]. Nov. 28, 1939 2,182,617 Michel Dec. 5, 1939 2,216,549 Deanesly Oct. 1, 1940 2,221,171 Story Nov. 12, 1940 2,421,951 Linn June 10, 1947 2,446,619 Stewart et al. Aug. 10, 1948 

2. A CYCLIC PROCESS WHICH COMPRISES CONVERTING PROPYLENE TO A MIXTURE OF POLYMERIC OLEFINS BOILING ABOVE ABOUT 325*F. AND BELOW ABOAUT 520* F. BY CONTACTING PROPYLENE WITH AN ACID POLYMERIZATION CATALYST IN A POLYMERIZATION ZONE, SEPARATING FROM THE REACTION MIXTURE A LOWER BOILING BUT NORMALLY LIQUID OLEFIN POLYMER FRACTION, RECYCLING SAID LOWER BOILING LIQUID POLYMER FRACTION TO THE POLYMERIZATION ZONE, RECOVERING FROM THE REACTION PRODUCTS A HIGHER BOILING MIXTURE OF POLYMERIC OLEFINS BOILING ABOVE 325*F., AND INHIBITING DECLINE IN CONVERSION RATE TO SAID HIGHER BOILING POLYMERIC OLEFIN MIXTURE BY REJECTING FROM THE POLYMERIZATION CYCLE A FRACTION COMPRISING SATURATED HYDROCARBONS FORMED IN SAID POLYMERIZATION ZONE. 